JPH05341107A - Optical material having inorganic coat film - Google Patents

Abstract

PURPOSE:To reform the surface conditions of an inorganic coat film and prevent clouding by reacting a specified silane compound with the inorganic coat film followed by graft polymerization with a material having aftertreatment or unsaturated bonding. CONSTITUTION:A silane compound having either one of a substitutent or unsaturated bonding to be converted into a hydrophilic group by aftertreatment is reacted with an inorganic coat film mainly containing SiO2. A material having aftertreatment or unsaturated bonding is successively graft-polymerized with it. Thus, the physical property of the inorganic coat film is changed, and the characteristic of the coat film is remarkably changed. When hydrophilic property is given to the surface by the aftertreatment, the contact angle of water is reduced, whereby fine water droplet is difficult to generate, and the clouding phenomenon by irregular reflection of light is prevented. Further, the electric conductivity of the surface is increased, whereby the charge on the surface is prevented, and dust is difficult to adhere to the coat film surface.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical material having an inorganic coating film whose surface state is modified, and a method for producing the same.

[0002]

2. Description of the Related Art Vacuum deposition method, ion plating method,
The inorganic coat film obtained by the sputtering method or the like is
It is widely used as an antireflection film for optical materials such as glasses and lenses, a hard coat film, and various functional films. Especially SiO
_{The two} films are widely used in terms of adhesion to the substrate, hardness, and ease of handling.

[0003]

[SUMMARY OF THE INVENTION] However, the inorganic coat film such as SiO _2, the cloudy water drops coat film surface on the optical material is produced by finely deposited by the temperature difference between the environment, the transmittance of the material is reduced There was a problem. In addition, there are various problems caused by the surface condition such that dust is easily attached due to surface charging. Therefore, the present invention solves such a problem, and an object thereof is to modify the surface condition of the inorganic coating film to solve one or more of the above-mentioned various problems. There is a function on the surface that can be resolved.

[0004]

The method for modifying the surface of an inorganic coated film according to the present invention comprises at least a substituent that can be converted into a hydrophilic group by post-treatment or an unsaturated bond in the inorganic coated film. It is characterized in that after a silane compound having one of them is reacted, it is post-treated or a substance having an unsaturated bond is graft-polymerized.

In order to treat the inorganic coating film, it is necessary to perform the treatment without deteriorating the properties, adhesion and durability of the coating film already existing on the substrate. For that purpose, it is necessary to carry out a reaction at a temperature and an environment that does not deteriorate the adhesion and durability, and at a temperature near the surface that does not affect the entire film, such as not affecting the spectral characteristics of the antireflection film. desirable. As the silane compound used in the present invention, a substance having a group capable of reacting with the film surface in the presence of a hydroxyl group can be used. For example, a halogenated silane compound may be mentioned.
The halogenated silane compound has a SiO 2 content in the presence of a hydroxyl group.
₍₂ ) A dehydrochlorination reaction as shown in the following formula occurs on the film surface, which is very effective for the reaction on the surface where hydroxyl groups exist.

[0006]

[Chemical 1]

Examples of the silane compound used in the present invention include vinyltrichlorosilane, 2-cyanoethyltrichlorosilane, allyltrichlorosilane, methylvinyldichlorosilane, ethoxymethyldichlorosilane, dimethoxymethylchlorosilane, divinyldichlorosilane and 3-cyanopropyltrichlorosilane. , Allylmethyldichlorosilane, dimethylvinylchlorosilane, diethoxydichlorosilane, 3-cyanopropylmethyldichlorosilane,
Allyldimethylchlorosilane, diallyldichlorosilane, 3-cyanopropyldimethylchlorosilane, phenylvinyldichlorosilane, 3-methacryloxypropylmethyldichlorosilane, allylphenyldichlorosilane, methylphenylvinylchlorosilane, diphenylvinylchlorosilane, and the like.

A silane compound having a substituent capable of being converted into a hydrophilic group by a post-treatment, or a silane compound having a hydrophobicity with a substituent capable of being converted into a hydrophilic group by a post-treatment is inorganic. After the reaction with the coat film, a hydrophilic treatment which is a post-treatment is performed, so that the surface of the coat film can have a function of having hydrophilicity or both hydrophilicity and hydrophobicity. As a post-treatment, another substance having a hydrophilic group may be reacted with the silane compound that has reacted with the coating film. If the hydrophilic property is given to the outermost surface by post-treatment and the hydrophobic group is located between the coat film and the hydrophilic group, the coat film has a complex function such as good wettability but not permeation of water molecules. Can be held by In this way, it is possible to simultaneously impart the contradictory functions to the coating film by post-treatment.

To react the silane compound with the inorganic coating film, the surface is coated with the silane compound by a Dip method, a spinner method, a spray method or the like, or a silane compound gas is coated with an inorganic coating in a vacuum atmosphere or in the air. A method of reacting with a film can be used. In the former case, the reaction is further promoted by optimally controlling the atmosphere during coating, for example, the humidity and the temperature, and the dipping time is preferably such that the reaction is sufficiently completed. Also,
It is more effective to accelerate the reaction by applying heat to the extent that it does not affect the characteristics of the coat film after coating. In the latter case, the silane compound gas may be introduced and reacted after forming the inorganic coating film in the vacuum chamber. Further, after forming the inorganic coat film, it is also possible to introduce a silane compound gas into a plasma atmosphere such as Ar gas and perform reactive vapor deposition, reactive ion plating or the like.

It is more effective to perform cleaning, chemical treatment, or plasma treatment on the surface of the inorganic coating film as a pretreatment for increasing the reactivity with the silane compound. The silane compound used in the reaction may be used alone or may be diluted with a solvent and used. In this case, it is preferable to use a solvent having no hydroxyl group from the viewpoint of liquid life. For example, as the solvent, toluene, methylene chloride, 1,3,3
-Trifluorotrichloroethane, trichlorethylene,
Tetrahydrofuran or the like can be used.

After the reaction is completed, the silane compound that has reacted with water molecules in the atmosphere and the silane compound that could not contribute to the reaction with the surface of the coating film are washed away to change the appearance such as antireflection properties before the treatment. It is possible to perform processing that does not exist.

As a cleaning method, after the reaction is completed, the reaction is carried out by cleaning with pure water or the like to treat the silane compound which cannot contribute to the reaction, and then toluene, methylene chloride, 1,3,3-trifluorotrichloroethane, trichloroethylene, It is more effective to wash with a solvent such as tetrahydrofuran.

The treatments described so far can be applied to the surface of the inorganic coating film mainly containing SiO ₂ .

[0014]

By reacting the inorganic coating film with a silane compound having a desired function, the physical properties of the surface of the inorganic coating film are changed and the characteristics of the coating film can be remarkably changed.

Further, when the surface is made hydrophilic, the contact angle of water is reduced, so that fine water droplets are less likely to be generated, the phenomenon of clouding due to irregular reflection of light can be prevented, and the electric conductivity of the surface is increased. , The surface is prevented from being electrified, and the surface of the coat film is less likely to have dust.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.

[0017]

【Example】

(Example 1) A synthetic resin lens made of a resin made of diethylene glycol bis (allyl carbonate) was washed with acetone, and then the surface of the synthetic resin lens was subjected to antireflection treatment by a vacuum deposition method at a substrate temperature of 50 ° C. The film composition is
SiO ₂ is lambda _0/4 from the lens side, ZrO ₂ layer and the total thickness of the SiO ₂ layer is lambda _0/4, ZrO ₂ layers λ _0/4, the top layer of the SiO ₂ layer has a lambda _0/4 .. The obtained lens with an antireflection film was washed with methylene chloride and immersed in a 99.9% divinyldichlorosilane solution for 2 minutes. After immersion, humidity 60
%, The lens was pulled up at a rate of 5 cm / min at a temperature of 15 ° C. and washed with a 99.9% methylene chloride solution. Next, the washed lens was heat-treated in 2N H ₂ SO ₄ at 60 ° C. for 1 hour to convert the vinyl group into a hydroxyethyl group. No change in appearance was observed after the treatment.

The following method was used for evaluating the obtained coat film.

Burnability: After tap water was applied to the surface of the coating film to dry it, the residue was wiped off with a cloth. When the residue remained, it was evaluated as C, when completely wiped off, it was evaluated as A, and when part of it remained, it was evaluated as B.

Abrasion resistance: 1 kg of cloth on the coat film surface
Was applied and rubbed 1000 times. The degree of scratches was evaluated in the following 3 grades.

A: There is no scratch.

B: 1 to 10 pieces, with fine scratches.

C: A number of fine scratches are made.

Adhesion: After dipping in pure water at 30 ° C. for 1 week, the adhesion of the coat film was examined. The adhesion of the coat film was measured by a cross cut tape test according to JIS D-0202. That is, using a knife, make cuts on the lens surface at intervals of 1 mm to make 100 squares of 1 mm ^2.
Form individually. Then, after strongly pressing the cellophane adhesive tape ("Cellotape" manufactured by Nitto Kagaku Co., Ltd.) on it, pulling and peeling it suddenly in a 90 ° direction from the surface,
The squares on which the coating film coating remained was used as the adhesion index.

Contact angle: Measured by a liquid-property method using a contact angle meter (CA-D type manufactured by Kyowa Scientific Co., Ltd.).

Anti-fogging property: Humidity of sample is 20%, temperature is 5 ° C.
Humidity of 80%, temperature of 30 ℃
The atmosphere was taken out, and the time at which the haze disappeared was measured.

Dustproofness: The half-life of the charged voltage was measured with a static Honest meter (manufactured by Shishido Shokai).
(Measurement conditions: temperature 25 ° C., relative humidity 60%) (Example 2) A lens made of diethylene glycol bis (allyl carbonate) washed with isopropyl alcohol was treated with a 5% sodium hydroxide aqueous solution at room temperature for 5 minutes, and The coating liquid described in 1 above was applied by a dipping method at a liquid temperature of 5 ° C. and a pulling rate of 40 cm / min. Next, in a hot air drying oven at 80 ° C for 30 minutes, 1
It was heat-cured at 30 ° C. for 2 hours.

The coating liquid was prepared as follows.

In a reaction vessel equipped with a stirrer, 206 parts of ethanol, 396 parts of ethanol-dispersed colloidal silica (“Oscar 1232” manufactured by Catalysts and Chemicals Co., Ltd., solid content 30%), and γ-glycidoxypropyltrimethoxysilane part A hydrolyzate (312 parts), a flow control agent (0.2 parts) (manufactured by Nippon Unicar Co., Ltd., "L-7604") and a 0.05N acetic acid aqueous solution (86 parts) were added, and the mixture was stirred at room temperature for 3 hours to obtain a coating liquid.

Example 1 was applied to the lens obtained as described above.
An antireflection treatment was performed in the same manner as in. Next, this lens is washed with acetone and set in a vacuum chamber, and the degree of vacuum is 0.1To.
It was evacuated and heated to rr and the substrate temperature of 50 ° C. Then, add 10 g of diphenylvinylchlorosilane to the vacuum chamber.
It was introduced into the vacuum chamber at a rate of c / min for 1 minute. After that, the lens was taken out into the atmosphere and washed with tetrahydrofuran. The lens after washing is washed in 2N H ₂ SO ₄ for 50 minutes.
The vinyl group was changed to a hydroxyethyl group by heat treatment at 30 ° C. for 30 minutes. No special abnormality was found in the appearance of the lens after the treatment.

(Comparative Example 1) The lens made of synthetic resin with antireflection before the divinyldichlorosilane treatment obtained in Example 1 was used as Comparative Example 1.

Comparative Example 2 The synthetic resin lens having an antireflection film before the diphenylvinylchlorosilane treatment obtained in Example 2 was used as Comparative Example 2.

The evaluation results of Examples and Comparative Examples are summarized in Table 1.
It was shown to.

[0034]

[Table 1]

[0035]

EFFECTS OF THE INVENTION Since the inorganic coating film is reacted with a silane compound capable of having hydrophilicity, the characteristics of the inorganic coating film and the surface are changed, and the effects such as prevention of fogging are remarkably improved. Was given.

The present invention can be applied to products using an inorganic coating film such as synthetic resin spectacle lenses, camera lenses, display panels, watch cover glasses and window glasses.

Claims (3)

[Claims] 1. An inorganic coating film is reacted with a silane compound having at least one of a substituent or an unsaturated bond which is converted into a hydrophilic group by post-treatment, and then post-treatment or unsaturated. An optical material having an inorganic coating film, which is obtained by graft-polymerizing a substance having a bond. 2. The inorganic coating film according to claim 1 is mainly composed of Si.
The optical material having an inorganic coat film according to claim 1, which is a single layer film or a multilayer film having a layer containing O ₂ as an outermost layer. 3. The inorganic coat film according to claim 1, wherein the inorganic coat film is an antireflection film formed on a synthetic resin lens or a synthetic resin lens having a hard coat layer. An optical material having a film.